WO2001081959A1 - Procede de production de film de retard - Google Patents

Procede de production de film de retard Download PDF

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Publication number
WO2001081959A1
WO2001081959A1 PCT/JP2001/003503 JP0103503W WO0181959A1 WO 2001081959 A1 WO2001081959 A1 WO 2001081959A1 JP 0103503 W JP0103503 W JP 0103503W WO 0181959 A1 WO0181959 A1 WO 0181959A1
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Prior art keywords
retardation film
polymer
polymers
retardation
film
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PCT/JP2001/003503
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English (en)
Japanese (ja)
Inventor
Akihiko Uchiyama
Masakazu Tsujikura
Takashi Kushida
Original Assignee
Teijin Limited
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Publication date
Application filed by Teijin Limited filed Critical Teijin Limited
Priority to EP01922045A priority Critical patent/EP1197768A4/fr
Priority to US10/018,139 priority patent/US6800697B2/en
Priority to JP2001578993A priority patent/JP4739636B2/ja
Publication of WO2001081959A1 publication Critical patent/WO2001081959A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to a method for manufacturing a retardation film. More particularly, the present invention relates to a method for producing a retardation film having a desired wavelength dispersion characteristic (wavelength dependence) with a high retardation with high productivity.
  • a retardation film is suitably used for, for example, an optical pickup used for a liquid crystal display device, a recording device, an optical device such as an optical recording medium, a light emitting element, an optical operation element, an optical communication element, and a touch panel.
  • a retardation film is used for a display device such as a liquid crystal display device, and has functions such as color compensation, a widening of a viewing angle, and anti-reflection.
  • a material of the retardation film generally, a polyether carbonate obtained by polycondensation of bisphenol A, or a thermoplastic polymer of polyethersulfone, polysulfone, polyvinyl alcohol, or norbornene resin is used.
  • the phase difference film is usually used in a liquid crystal display device of a single part is nematic (STN) mode for the purpose of color compensation and expansion of a viewing angle.
  • STN nematic
  • the method for producing this retardation film the following method is known as a method for producing a mixture of two polymers.
  • Japanese Patent Application Laid-Open No. H11-91402 describes a method for producing a retardation film by mixing a polymer that generates positive birefringence and a polymer that generates negative birefringence. Specifically, a film formed by mixing poly (2,6 dimethyl-1,4 phenylene oxide) and polystyrene, or a film formed by mixing polyvinyl chloride and polymethyl methacrylate is uniaxially stretched. It is described that a retardation film having small viewing angle dependence was obtained.
  • Japanese Patent No. 2878090 describes a retardation film 'obtained by uniaxially stretching a mixture or copolymer film of at least two kinds of polymers.
  • a method is disclosed in which polymers having different photoelastic constants are combined. Specifically, it is described that polystyrene and polypropylene were mixed at a ratio of 1: 2.6.
  • Japanese Unexamined Patent Publication No. Hei 6-1747942 discloses that two poly-forces whose photoelastic constant satisfies a specific relationship.
  • a retardation film formed of a composition obtained by mixing a component resin is described.
  • the main components are bisphenol A-type polycarbonate resin and bisphenol A derivative in which two methyl groups at the central carbon of bisphenol A are substituted with phenyl groups, and a small amount of bisphenol A is used. It is described that the raw material contained was mixed with the polycarbonate resin obtained.
  • the retardation film is optically designed so as to exhibit a function of generating circularly polarized light in combination with the polarizing plate.
  • Hei 6-230368 describes a retardation film having a birefringence of zero at a certain wavelength of visible light.
  • Such retardation films are formed by laminating two retardation films having different retardation wavelength dependences or different photoelastic constants in a certain direction, a mixture of a plurality of polymers, or a copolymer. It is described that it can be obtained by a stretching method.
  • Japanese Patent Application Laid-Open No. 5-271119 describes that two birefringent films having a specific retardation are laminated and manufactured.
  • Japanese Patent No. 2609139 discloses that two or more specific birefringent films having different wavelength differences in retardation are laminated at a specific angle to produce the film.
  • a main object of the present invention is to provide a method for manufacturing a retardation film that easily and highly controls the wavelength dispersion characteristic of the retardation.
  • Another object of the present invention is to provide a method of manufacturing a retardation film that can promptly respond to various requests for chromatic dispersion characteristics from customers.
  • a further object of the present invention is to provide a method for easily producing one retardation film formed of the same kind of polymer with high productivity. Disclosure of the invention
  • the present inventors have focused on a method of mixing two polymers, and have a method of easily manufacturing a retardation film having a desired wavelength dispersion characteristic with a retardation in a controlled manner.
  • a polymer material for a retardation film was intensively studied.
  • the compatibility between the polymers used is considered while taking into account the extremely high optical properties such as high transparency and high optical homogeneity required for the retardation film, high mechanical properties, easy handling, and good film forming properties. I thought it was very important.
  • the present invention adjusts the mixing ratio of polymers A and B that are compatible with each other and satisfy the following (1) to (2) so that the retardation has a desired wavelength dispersion characteristic.
  • a method for producing a retardation film which is characterized by being formed into a film.
  • Polymer A is a copolymer composed of repeating units a and b
  • the polymer B is a copolymer composed of repeating units a and b, and has a copolymer composition different from that of the polymer A.
  • the present invention at least two types of polymers A and B compatible with each other are mixed.
  • the polymers A and B are copolymers having at least two common repeating units.
  • the wavelength dispersion characteristics of both retardations are not the same.
  • two polymers having different properties are mixed to control the properties. In other words, when the retardation film is formed alone, the wavelength dispersion of the retardation is not all the same, and two or more types of compatible polymers are mixed.
  • both polymers A and B have positive optical anisotropy, and the former R (450) ZR (550) is 1.06 and the latter is R (450 ) / R (550) is 0.25 by mixing the two polycarbonate copolymers while adjusting the mixing ratio.
  • a retardation film having an arbitrary retardation wavelength dispersion up to 1.06 can be obtained.
  • the retardation film since the retardation film must be transparent, it is important that the polymers A and B to be mixed are compatible (compatible) with each other.
  • compatible means that the haze value of the retardation film formed from the obtained mixture is 20/0 or less.
  • the haze value is preferably 1% or less, more preferably 0.5% or less.
  • the retardation of the retardation film is such that light passes through the retardation film with thickness d.
  • the orientation direction will be described later.
  • the chromatic dispersion (wavelength dependence) of the retardation is the chromatic dispersion (wavelength dependence) of the birefringence ⁇ ⁇ .
  • the optical anisotropy is positive when the refractive index in the orientation direction in the plane of the retardation film is larger than the refractive index in the direction perpendicular to the orientation direction, and the optical anisotropy is when the refractive index is small. Is defined as negative.
  • the orientation direction of the retardation film is determined by stretching an unstretched film. When the glass transition temperature of the polymer forming the film is ⁇ g , and the film is stretched in one direction under a temperature condition near T g (T g — in the range of 5 ° C to T g +20 ° C) Is the direction of stretching.
  • phase difference refers to the absolute value of the phase difference.
  • the optical anisotropy is negative, the phase difference is negative, but the sign of the sign is ignored in the present invention unless otherwise specified.
  • the wavelength for determining the sign of the optical anisotropy is 550 nm.
  • a retardation film having a desired retardation wavelength dispersion characteristic can be easily controlled by controlling a mixing amount of at least two kinds of polymers _A and B. Can be provided.
  • Polymers A and B may have different optical anisotropy (ie, a combination of positive and negative) and may be the same, that is, both may be positive or both may be negative.
  • polymer is positive or negative” or “phase retardation wavelength dispersion of polymer” is abbreviated expression, and in fact, “optical anisotropy of a retardation film composed of a polymer” is actually used. Positive or negative ”and“ wavelength dispersion of retardation film of polymer ”.
  • Polymers A and B each have a positive optical anisotropy or a negative optical anisotropy when a phase film is formed independently, that is, the optical anisotropy of a retardation film formed from polymer A
  • the anisotropy and the optical anisotropy of the retardation film formed from the polymer B are preferably positive and positive or negative and negative.
  • the optical anisotropy is determined by preparing an unstretched film from the polymer A by a solution casting method, and then forming the unstretched film near T s (from T g—5 ° C to T g + 1.1 to 3 times in one direction under the temperature condition of 20 ° C) Is evaluated using a retardation film obtained by stretching the film.
  • the wavelength dispersion of the retardation is not all the same. That is, the wavelength dispersion of retardation in the retardation film (retardation film A) formed of polymer A alone and the wavelength dispersion characteristic of retardation in the retardation film (retardation film B) formed of polymer B alone are: different.
  • one of the retardation film A and the retardation film B has a wavelength dispersion characteristic of retardation satisfying the following expression (1).
  • R (450) and R (550) are the in-plane retardations of the retardation film measured at the measurement light wavelengths of 450 nm and 550 nm, respectively.
  • the polymer A or B is selected so that the retardation film composed of the polymer A alone satisfies the above formula (1), and the retardation film composed of the polymer B alone satisfies the following formula (2). Is more preferred.
  • the chromatic dispersion of the phase difference is in a range from a certain value of less than 1 to a certain value of 1 or more. In this case, it can be easily obtained only by appropriately changing the mixing ratio of the polymers A and B.
  • the degree to which the wavelength dispersion of retardation in the retardation film formed of polymer A alone and the wavelength dispersion of retardation in the retardation film formed of polymer B alone are different is R (450) / R (550) Is preferably not less than 0.1.
  • the difference between R (450) and R (550) is preferably 0.15 or more, and more preferably 0.2 or more. Is more preferred. This is because the larger the difference, the wider the range for controlling the wavelength dispersion of the retardation film. If the optical anisotropy of the polymers A and B is positive and negative, the signs are different, so this is not the case. In the positive and negative cases, it is possible to produce a retardation film having a wide range of wavelength dispersion depending on the mixing ratio of the two even if the difference between the two is not widened. Next, the polymers A and B used in the present invention will be described.
  • Polymers A and B are copolymers comprising repeating units a and b. However, polymers A and B differ in the content of repeating units a and b. That is, the copolymer compositions of Polymers A and B are not the same.
  • the copolymer composition is not particularly limited as long as the polymers A and B are compatible.
  • the sequence in the polymer is not particularly limited as long as the polymers A and B are compatible with each other, and may be a random copolymer or a block copolymer. Further, the polymers A and B may have at least one of them (this may have a repeating unit c other than the repeating units a and b as a copolymer component).
  • one or more third polymers may be used in combination if they are compatible with A and B.
  • the third polymer is preferably a thermoplastic polymer from the viewpoint of moldability of the retardation film.
  • thermoplastic polymers used in the present invention are compatible with each other, and are not particularly limited as long as the above conditions are satisfied. However, they have excellent heat resistance, good optical performance, and good film formation. It is preferable to select a thermoplastic polymer having a function and capable of forming a film by a melt extrusion method or a solution casting method.
  • thermoplastic polymers include, for example, aromatic polyester polymers, polyolefins, polyethers, polysulfones, and polyethersulfones.
  • aromatic polyester polymers such as polyarylate, polyester, and polycarbonate have excellent heat resistance, film forming properties, and optical properties.
  • poly-ponate is more preferable in terms of transparency, heat resistance, film forming property, and productivity.
  • Polymers A and B are advantageous because a combination of the same types of polymers among the thermoplastic polymers is particularly excellent in compatibility.
  • a copolymer containing a structure having a fluorene skeleton (for example, containing 1 to 99 mol% of the whole) has heat resistance, film forming property, and low photoelastic constant. It has good balance as a retardation film. Therefore, it is preferable that the polymers A and B have a structure in which at least one of the repeating units a and b has a fluorene skeleton. More preferably, at least one of the repeating units a and b is a component derived from bisphenol having a fluorene ring. More preferably, it is extremely advantageous from the viewpoint of compatibility that both the repeating units a and b are such components.
  • the bisphenol component having such a fluorene ring is represented by the following formula.
  • the hydrogen atom of the benzene ring in the above formula may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, such as an alkyl group or an aryl group, or a halogen atom.
  • the ratio of the repeating units a and b in the polymers A and B is not particularly limited as long as the polymers A and B are compatible.
  • the properties such as the optical properties of the retardation film are mainly determined by the structure and content of the repeating units a and b contained in the mixture of the polymers A and B. Therefore, the ratio of the repeating units a and b of the two polymers A and B to be used and the mixing amount of the polymers A and B may be appropriately determined so that a retardation film having desired characteristics is obtained. .
  • repetition rate of the unit a and b in the polymer one A is, a 1 to 9 9 mole 0/0, more preferably 1 0-9 0 mole 0 / o, especially preferably 5 0-9 0 mol 0 / in the range of o, b force "9 9-1 mole 0 / o range, good re preferably 9 0-1 0 mole 0 / o, especially preferably 9 0-5 0 mol% of the range, respectively Can be determined.
  • polycarbonate copolymers that can be preferably used as the polymers A and B are specifically represented by the following formula (I)
  • F ⁇ Rs is each independently at least one selected from a hydrogen atom, a halogen atom and a hydrocarbon group having 1 to 6 carbon atoms, and X is
  • R 9 to R 16 are each independently at least one selected from a hydrogen atom, a halogen atom and a hydrocarbon group having 1 to 22 carbon atoms, and Y is
  • R 21 ⁇ Pi R 22 each independently represent a hydrogen atom, a hydrocarbon group of a halogen atom and a carbon number 1 to 22 of ⁇
  • R 20 and R 2 3 is independently at least one group selected from hydrocarbon groups having 1 to 20 carbon atoms
  • Ar to Ar 3 are each independently an aryl group having 6 to 10 carbon atoms.
  • F ⁇ Rs is independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group having 1 to 6 carbon atoms.
  • the hydrocarbon group having 1 to 6 carbon atoms include an alkyl group such as a methyl group, an ethyl group, an isopropyl group and a cyclohexyl group, and an aryl group such as a phenyl group. Of these, a hydrogen atom and a methyl group are preferred.
  • R 9 to R 16 are each independently at least one group selected from a hydrogen atom, a halogen atom and a hydrocarbon group having 1 to 22 carbon atoms.
  • a hydrocarbon group having 1 to 22 carbon atoms include an alkyl group having 1 to 9 carbon atoms such as a methyl group, an ethyl group, an isopropyl group and a cyclohexyl group, a phenyl group, a biphenyl group and a terphenyl group.
  • Aryl group Of these, a hydrogen atom and a methyl group are preferred.
  • R 17 to R 19 , R 21 and R 22 are each independently at least one group selected from a hydrogen atom, a halogen atom and a hydrocarbon group having 1 to 22 carbon atoms. Examples of such a hydrocarbon group include the same as those described above.
  • R 20 and R 2 3 is at least one group selected from each independently a hydrocarbon group having 1 to 20 carbon atoms, for such hydrocarbon group include the same as those described above.
  • a ri to Ar 3 are each independently a phenyl group having 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group.
  • the retardation film made of the polycarbonate copolymer having a fluorene skeleton described above has a wavelength dispersion characteristic of retardation R (450) no R (550) ⁇ 1 depending on the composition ratio of the fluorene component, and R (450) Some have R (550) ⁇ 1.
  • the copolymer composition (molar ratio) of the fluorene component in the polyacrylonitrile copolymer and the repeating units a and b in the mixture of the polymers A and B can be determined by, for example, a nuclear magnetic resonance (NMR) apparatus. .
  • NMR nuclear magnetic resonance
  • the above polycarbonate has the following formula
  • R 24 and R 25 are each independently at least one group selected from the group consisting of a hydrogen atom and a methyl group.
  • R 26 and R 27 are each independently at least one selected from a hydrogen atom and a methyl group, and Z is a group of the following formula
  • Polycarbonate copolymers in which the repeating unit represented by) occupies 90 to 10 mol% of the whole are particularly preferred in terms of heat resistance, transparency and the like.
  • a method for producing the above polycarbonate copolymer a method by polycondensation of a dihydroxy compound such as bisphenol with a phosgene or a carbonate-forming compound such as diphenyl carbonate, a melt polycondensation method and the like are preferable.
  • the intrinsic viscosity of the polycarbonate copolymer is preferably 0.3 to 2.0 OdlZg. If it is less than 0.3, there is a problem that brittle re-mechanical strength cannot be maintained. If the viscosity exceeds this, the viscosity of the solution becomes too high, which may cause problems such as generation of die lines in solution film formation and difficulty in purification at the end of polymerization.
  • a phase difference film having a desired wavelength dispersion characteristic is provided by adjusting the mixing ratio of the above polymers A and B and forming the mixture into a film.
  • the method of mixing the polymers A and B by adjusting the mixing ratio of the polymers A and B may be melt mixing or may be performed in a solvent in which A and B are dissolved.
  • the solution casting method is preferred for the following reasons. Therefore, it is preferable to mix in a solvent in which A and B are dissolved, and then to form a film by a solution casting method.
  • the mixing ratio of the polymers A and B is not particularly limited, but as described above, the optical characteristics of the retardation film are determined by the repeating units a and b contained in the mixture of the polymers _A and B. The contribution of the structure and content is large. Therefore, the mixing amount of the polymers A and B is appropriately determined in consideration of the ratio of the repeating units a and b constituting the polymers A and B.
  • the polymer A is in the range of 1 to 99% by weight, preferably 5 to 95% by weight, more preferably 10 to 90% by weight, and the polymer is said to be 99 to 1% by weight, preferably It is in the range of 95 to 5% by weight 0 / o, more preferably 90 to 10% by weight.
  • Polymer one proportion of the recurring units (a) based on the total amount of repetitions units a and b contained in the mixture of A and B is 5 0-9 9 mol 0/0, preferably 5 0-9 5 mol 0 / Determine to be o.
  • the value should be determined in consideration of the amount of c.
  • the resulting mixture is then formed into a film by, for example, a melt extrusion method or a solution casting method.
  • a solution composition obtained by dissolving the mixture in a solution is cast into a film by a casting method in which a die is extruded from a die onto a stainless steel belt / film belt, a doctor knife method, etc. If necessary, the film is stretched to obtain a retardation film so as to have optical characteristics such as a gradation.
  • the solution casting method is preferred because the film thickness unevenness is reflected in the retardation unevenness, and the inclusion of foreign matter is not allowed.
  • the solution casting method comprises the steps of dissolving polymers A and B in an organic solvent to produce a solution composition (dissolution step), casting the solution composition on a support (casting step), and Drying the cast solution composition containing the organic solvent (drying step).
  • dissolution step dissolving polymers A and B in an organic solvent to produce a solution composition
  • casting step casting the solution composition on a support
  • drying step Drying the cast solution composition containing the organic solvent
  • a solution composition is usually prepared using a solvent that dissolves the polycarbonate.
  • a solvent include, but are not particularly limited to, haloalkanes such as methylene chloride, chloroform, and 1,2-dichloroethane; cyclic ethers such as tetrahydrofuran, 1,3-dioxolan, and 1,4-dioxane; Ketones such as tyl ketone, methyl isobutyl ketone and cyclohexanone, and aromatic hydrocarbons such as chlorobenzene are used.
  • methylene chloride and dioxolan are preferred from the viewpoint of solubility and stability of the solution composition.
  • the concentration of the polymer in the solution composition is usually 1 to 50% by weight.
  • concentration depends on the molecular weight of the polymer (viscosity) used, 5-4 0 weight 0/0, 'preferably 1 0-3 0% by weight.
  • the solution composition contains various ultraviolet absorbers such as phenylsalicylic acid, 2-hydroxybenzophenone, and triphenyl phosphate, a blueing agent for changing the color, and an antioxidant. May be added. Further, an additive such as a plasticizer may be added. In this case, the amount is preferably 10% by weight or less, more preferably 3% by weight or less based on the solid content of the polymer.
  • the solution composition is cast on a support such as a stainless steel belt or a film belt.
  • the solvent is gradually removed from the casting on the belt, and when the amount of the solvent contained in the casting reaches about 15 to 20% by weight, the casting is peeled off from the support. Then, the solvent-containing film peeled from the support is continuously treated in the next drying step.
  • the drying step can be performed, for example, by dividing into the following first to third steps.
  • the film containing the solvent is usually transported for several minutes to one hour while the ambient temperature is set to 15 to 40 ° C., and the drying is promoted, so that the residual solvent concentration in the film is reduced to 10 to 10. It can be up to 15% by weight.
  • the film is fed into a pin tenter, and both ends are gripped and fixed by a pin sheet, and conveyed while heating.
  • the heating temperature and the reduction ratio of the pin tenter rail are It is a predetermined value.
  • the concentration of the solvent remaining in the film can be adjusted to 3 to 5% by weight by drying the film while usually transporting the film for several minutes to several ten minutes.
  • the film is passed through a dryer such as a roll hanging type to give a desired temperature and tension to be processed.
  • a dryer such as a roll hanging type
  • methylene chloride used as the solvent
  • a small amount of methylene chloride may remain in the dried film.
  • the residual amount at that time is preferably 0.5% by weight or less, more preferably 0.3% by weight or less, and even more preferably 0.1% by weight or less.
  • the residual amount varies depending on the desired optical properties, but is preferably 0.3 to 2% by weight.
  • the obtained retardation film is an unstretched film, it is stretched so as to have a desired retardation as needed. It may be selected depending on the application.
  • the stretching conditions are usually 1.05 to 3 times when the film temperature is in the range of Tg ⁇ 10 ° C.
  • the thickness of the obtained retardation film is preferably from 5 m to 200 m, more preferably from 10 to 12 OjUm.
  • a film having optical anisotropy generally gives a different phase difference value to obliquely incident light as compared with frontally incident light.
  • the three-dimensional refractive index of the polymer material is represented by nx, ny, nz, and the definition of each is
  • n X refractive index in the main orientation direction in the film plane
  • n y Refractive index in the direction perpendicular to the main orientation direction in the film plane
  • n z Refractive index of the film surface in the normal direction
  • the main orientation direction means, for example, the flow direction of the film, and chemically indicates the direction in which the polymer main chain is oriented.
  • the optical anisotropy when nx> nz, the optical anisotropy is positive, and when nx ⁇ nz, the optical anisotropy is negative.
  • the three-dimensional refractive index is measured by an ellipsometry, which is a technique for analyzing the polarization state of outgoing light obtained by entering polarized light into a film.
  • the optical anisotropy of the film is regarded as a refractive index ellipsoid, and the three-dimensional refractive index is determined by a known method of calculating the refractive index ellipsoid. Since the three-dimensional refractive index has a wavelength dependence of the light used, it is preferable to define the three-dimensional refractive index by the light source wavelength used. As a method of expressing optical anisotropy using the three-dimensional refractive index, the following equation (3)
  • N z (n x— n z) / (n x— n y) (3)
  • the slow axis of the film having positive optical anisotropy is nx and the fast axis is ny.
  • two polymers A and B which are compatible with each other and satisfy the following (1) to (4) so that the phase difference has a desired wavelength dispersion characteristic. And a method for producing a retardation film in which the mixture ratio is adjusted and the mixture is formed into a film.
  • Polymer A is a polyacrylonitrile copolymer composed of repeating units a and b.
  • Polymer B is a polyacrylonitrile copolymer composed of repeating units a and b.
  • the repeating unit a contains a bisphenol component having a fluorene ring
  • the mixing ratio of the polymers A and B is determined based on the total amount of the repeating units a and b contained in the mixture so that the ratio of the repeating unit a is 50 to 99 mol%.
  • the polymer A has a repeating unit a represented by the above formula (III) (where R 24 and R 25 are methyl groups) and a repeating unit b represented by the above formula (IV). (Wherein Z is an isopropylidene group), and the repeating unit represented by the above formula (I11) is 50 to 90 mol%.
  • the repeating unit represented by the formula (IV) is 50 to 10 mol%.
  • the repeating units a and b are the same as the polymer A, the repeating unit represented by the above formula (III) is 20 to 60 mol%, and the repeating unit represented by the above formula (IV) Is from 80 to 40 mol%.
  • Polymer one A and B Mixing ratio of polymer one A and B, polymer A 1 to 99 wt%, the polymer one B is 99 to 1 wt. 0/0.
  • polymer A is 20-97% by weight 0 / o and polymer B is 80-3% by weight. More preferred details, the polymer A is 30 to 95 weight 0 / o, the polymer B is from 70 to 5 weight 0 / o.
  • Polymer A has a positive optical anisotropy when formed into a retardation film by itself, and polymer B has a positive optical anisotropy.
  • the retardation film produced by the production method of the present invention preferably has a wavelength dispersion of the retardation satisfying the above formula (1), and has various retardation wavelength dispersions. I can get Therefore, for example, a color compensation film of a liquid crystal display device, a viewing angle widening film, a reflection type liquid crystal display device, a retardation film for a circularly polarizing plate of an antireflection film, and a retardation film used for optical pickup of an optical recording device.
  • the polymer A and the polymer B are composed of a mixture of mutually compatible polymers A and B, and the polymer A and the polymer B are represented by the following (1) to (2)
  • a phase difference film of high optical quality, in which the wavelength dispersion of the phase difference is highly controlled, is satisfied.
  • the polymer A is a copolymer composed of repeating units a and b,
  • Polymer B is a copolymer composed of repeating units a and b, and has a copolymer composition different from that of polymer A.
  • the polymers A and B are aromatic polyester polymers.
  • the mixing ratio of the polymers A and B is such that the proportion of the repeating unit a is 50 to 99 based on the total amount of the repeating units a and b contained in the composition. It has been determined to be mol%.
  • the retardation film is a polymer copolymer in which the polymers A and B are composed of repeating units a and b, wherein the repeating unit a is a bisphenol component having a fluorene ring.
  • the repeating unit a is a bisphenol component having a fluorene ring.
  • port Rimmer a is 1 to 99 wt%
  • the polymer B is from 99 to 1 weight 0/0
  • contained in the mixture proportion of the repeating unit a is 50 to 90 mol% der Li
  • the proportion of the repeating unit b is 50 to 1 0 molar 0 / o.
  • the polymers A and B each have a positive optical anisotropy or a negative optical anisotropy when the retardation film is formed alone.
  • each of the polymers A and B has a difference of R (450) ZR (550) of at least 0.1 when the retardation film is formed alone (however, R (450) and R (550) Is the retardation in the film plane of the retardation film measured at the measurement light wavelength of 450 nm and 550 nm, respectively).
  • the retardation R value and the ⁇ value which are the product of the birefringence ⁇ of the retardation film and the film thickness d, were measured by using a spectroscopic ellipsometer “M150” manufactured by JASCO Corporation. The R value was measured with the incident light and the surface of the retardation film orthogonal to each other.
  • the total light transmittance and the haze value of the retardation film were measured by an integrating sphere light transmittance measuring device according to Japanese Industrial Standards JIS K 7105 “Testing method of optical properties of plastic”.
  • a color difference / turbidity meter “G0H-300A” manufactured by Nippon Denshoku Industries Co., Ltd. was used as an evaluation device.
  • the thickness of the retardation film was measured with an electronic micro manufactured by Anritsu Corporation.
  • the measurement was carried out by means of proton NMR of “JNM-aIpha600” manufactured by JEOL Ltd.
  • heavy benzene was used as a solvent, and calculation was performed from the proton intensity ratio of each methyl group.
  • aqueous sodium hydroxide solution and ion-exchanged water were charged into a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser.
  • the monomers [A] and [B] having the above-mentioned structure were dissolved at a predetermined molar ratio shown in Table 1, and a small amount of hydrosulfite was added thereto to prepare a reaction solution.
  • methylene chloride was added to this.
  • the temperature of the reaction solution was 20 ° C. Phosgene was blown into this for about 60 minutes. Further, p-tert-butylphenol was added to emulsify, and then triethylamine was added, followed by stirring at 30 ° C.
  • the obtained two copolymers were each dissolved in methylene chloride to prepare a solution composition having a solid content of 20% by weight.
  • This solution composition was cast on stainless steel, heated while gradually increasing the temperature from 15 ° C., peeled off from the stainless steel, and further dried to produce a cast film.
  • the film obtained at this time had an R value of 10 nm or less.
  • the film also contained 0.9% by weight of methylene chloride.
  • Copolymers 1 and 2 produced in the above Synthesis Examples were dissolved in methylene chloride at a predetermined mixing ratio (parts by weight) shown in Table 2 to prepare a solution composition having a solid content of 20% by weight.
  • This solution composition was cast on stainless steel, heated while gradually increasing the temperature from 15 ° C., peeled from the stainless steel, and dried to produce a cast film.
  • the film obtained at this time had an R value of 1 O nm or less.
  • the film also contained 1 weight 0 / o of methylene chloride.
  • B content ratio in Table 2 is the ratio of the monomer unit B in the total mixture of Copolymer 1 and 2 (mol 0/0). '
  • the obtained two copolymers (copolymers 3 and 4) were each dissolved in methylene chloride to prepare a solution composition having a solid content of 20% by weight.
  • This solution composition was cast on stainless steel, and then heated while gradually increasing the temperature from 15 ° C, peeled off the stainless steel, and further dried. A cast film was produced.
  • the film obtained at this time had an R value of 10 nm or less.
  • the film also contained 1% by weight of methylene chloride.
  • the copolymers 1, 3 produced in Synthesis Examples 3 and 4 were dissolved in methylene chloride at a predetermined mixing ratio (parts by weight) shown in Table 3 to prepare a solution composition having a solid content of 20% by weight. .
  • the solution composition was cast on stainless steel, heated while gradually increasing the temperature from 15 ° C., peeled from stainless steel, and dried to prepare a cast film.
  • the film obtained at this time had an R value of 10 nm or less. Also the film contained 1 wt 0/0 of methylene chloride.
  • Polycarbonate copolymers 5, 6, and 7 were produced in the same manner as in Synthesis Example 1 except that predetermined amounts of monomers [A] and [B] shown in Table 5 were used.
  • the composition ratios of the obtained copolymers 5, 6, and 7 were analyzed in detail by the proton NMR method described above, the repeating units of monomer [B] contained 70% in each copolymer. 4, 31.7 and 66.9 mol%.
  • the film obtained at this time had an R value of 10 nm or less.
  • the film also contained 1% by weight of methylene chloride.
  • Table 6 summarizes the characteristics of these retardation films.
  • the B content ratio in Table 6 is the ratio (mol%) of monomer B per unit.
  • copolymers 5 and 6 produced in the above Synthesis Examples were mixed with the predetermined mixing ratios shown in Table 7 so that the content of the monomer units [ ⁇ ] and [ ⁇ ] in the retardation film 8 of Reference Example 1 was the same. At a rate (parts by weight). Next, a cast film was produced in the same manner as in Example 1 above. The film obtained at this time had an R value of 10 nm or less. The film also contained 1% by weight of the solvent.
  • Table 6 summarizes the properties of this retardation film.
  • the B content ratio in Table 6 is the ratio (mol 0 / o) of the monomer unit B in the entire mixture of copolymers 5 and 6.
  • Table 7
  • the wavelength dispersion characteristic of the retardation in the obtained retardation film 9 was the same as that of the retardation film 8 obtained in Reference Example. As described above, it was found that according to the production method of the present invention, a retardation film having the same characteristics as a retardation film produced from one copolymer was obtained.
  • the retardation film 8 of Reference Example 1 and the retardation film 9 have the same content of the monomer unit B as viewed from the proton R.
  • the difference between the two is that the polymer material constituting the retardation film 8 is one copolymer, but that of the retardation film 9 is a blend of the two copolymers.
  • the structure of the polymer material was analyzed using 13 C-NMR. This evaluation method takes advantage of the fact that the chemical shift of the carbonyl carbon in the carbonate bond between monomers [A] and [A], [A] and [B], and [B] and [B] is different. is there. In Table 8, these diploid structures are described as [A]-[A], [A]-[B], [B]-[B]. As can be seen from Table 8, in these polymer materials, it was found that the ratios at which the above three structures exist were different.
  • the retardation film is formed from one copolymer or has two repeating units that are the same as the repeating units of the copolymer, and each of the repeating units has It was possible to discriminate by evaluating in this way whether the copolymer was formed by blending two types of copolymers having different content ratios.
  • Such an evaluation method is called Polycarbonate It is presumed that it is possible to distinguish between a blend and a copolymer even in the case of a polymer other than a acrylate.
  • a retardation film having various retardation wavelength dispersion characteristics can be provided with high productivity by using a simple method of mixing at least two compatible polymers.
  • a phase difference film is produced by adjusting the mixing ratio of at least two types of polymers A and B that are mutually compatible with each other to form a film of the mixture.
  • the polymers A and B are copolymers composed of two common repeating units and having different copolymer compositions.
  • the retardation wavelength dispersion of the retardation film of the polymer A and the retardation of the polymer B A retardation film having a desired wavelength dispersion can be industrially and easily produced within a wide range from the retardation wavelength dispersion of the film.
  • the chromatic dispersion of the phase difference can be controlled to a high degree, and a high-quality phase difference film can be provided. It is very valuable as a method for providing a phase difference film applied to a display input device such as a display device using a liquid crystal or a touch panel.

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  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
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  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
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Abstract

La présente invention concerne un procédé de production d'un film de retard. Ce procédé consiste à mélanger, dans des proportions régulées, au moins deux polymères (A) et (B), qui sont compatibles l'un avec l'autre, et à travailler le mélange résultant sous forme de film. Les polymères (A) et (B) sont des copolymères comprenant deux types d'unités de répétition communes, qui diffèrent l'une de l'autre dans la proportion d'unités de monomère. Le procédé selon cette invention permet de produire, de manière aisée et industrielle, un film de retard qui présente une dispersion des longueurs d'onde souhaitée. La dispersion des longueurs d'onde de retard peut être hautement régulée, ce qui permet d'obtenir un film de retard de grande qualité.
PCT/JP2001/003503 2000-04-24 2001-04-24 Procede de production de film de retard WO2001081959A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP01922045A EP1197768A4 (fr) 2000-04-24 2001-04-24 Procede de production de film de retard
US10/018,139 US6800697B2 (en) 2000-04-24 2001-04-24 Process for producing retardation film
JP2001578993A JP4739636B2 (ja) 2000-04-24 2001-04-24 位相差フィルムの製造方法

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JP2000122489 2000-04-24
JP2000-122489 2000-04-24

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EP (1) EP1197768A4 (fr)
JP (1) JP4739636B2 (fr)
KR (1) KR100487701B1 (fr)
CN (1) CN1201171C (fr)
TW (1) TW533323B (fr)
WO (1) WO2001081959A1 (fr)

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WO2006107006A1 (fr) * 2005-03-31 2006-10-12 Teijin Limited Plaque transparente
WO2007074892A1 (fr) * 2005-12-26 2007-07-05 Teijin Limited Film transparent
JP2017115119A (ja) * 2015-12-24 2017-06-29 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． 重合体、補償フィルム、光学フィルム及び表示装置
US10035889B2 (en) 2013-04-03 2018-07-31 Mitsui Chemicals, Inc. Optical film

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US20030043730A1 (en) * 2000-03-29 2003-03-06 Akihiko Uchiyama Protecting film for optical recording medium and optical recording medium
CA2459177A1 (fr) * 2002-06-27 2004-01-08 Teijin Limited Film oriente a base de polycarbonate et film a dephasage
KR100526402B1 (ko) * 2002-11-22 2005-11-08 주식회사 엘지화학 고리형 올레핀계 부가 중합체를 포함하는 네가티브Ｃ-플레이트(ｎｅｇａｔｉｖｅ Ｃ-ｐｌａｔｅ)형 광학이방성 필름 및 이의 제조방법
TW200500746A (en) 2002-12-19 2005-01-01 Nitto Denko Corp Birefringent optical film, elliptically polarizing plate using the same, and liquid crystal display using the same
TW200506467A (en) * 2002-12-19 2005-02-16 Nitto Denko Corp Birefringent optical film, elliptically polarizing plate using the same, and liquid crystal
KR100981901B1 (ko) 2002-12-20 2010-09-13 데이진 가부시키가이샤 투명 도전성 적층체, 터치패널 및 터치패널 부착액정표시장치
US7508474B2 (en) * 2003-04-07 2009-03-24 Dai Nippon Printing Co., Ltd. Laminated retardation layer, its fabrication process, and liquid crystal display incorporating the same
US6937310B2 (en) * 2003-05-16 2005-08-30 Eastman Kodak Company Compensation films for LCDs
EP1788004B1 (fr) * 2004-07-16 2013-10-23 Nitto Denko Corporation Nouveau polymère modifié, procédé pour le fabriquer, et utilisation dudit nouveau polymère modifié
EP1791005A1 (fr) * 2004-09-15 2007-05-30 Teijin Limited Film a retard de flamme
KR101205743B1 (ko) 2004-11-11 2012-11-28 스미또모 가가꾸 가부시끼가이샤 광학 필름
WO2006082818A1 (fr) * 2005-02-03 2006-08-10 Fujifilm Corporation Plaque polarisante et dispositif d'affichage a cristaux liquides
CN101680990B (zh) * 2007-06-01 2013-09-04 帝人株式会社 相位差膜、叠层偏振光膜及液晶显示装置
CN101617249B (zh) 2007-08-14 2014-07-09 Lg化学株式会社 光学膜及制备该光学膜的方法
JP4881340B2 (ja) * 2008-03-24 2012-02-22 富士フイルム株式会社 光学フィルム、偏光板及び液晶表示装置
JP6830157B2 (ja) 2017-06-28 2021-02-17 富士フイルム株式会社 位相差フィルム

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
WO2006107006A1 (fr) * 2005-03-31 2006-10-12 Teijin Limited Plaque transparente
WO2007074892A1 (fr) * 2005-12-26 2007-07-05 Teijin Limited Film transparent
US10035889B2 (en) 2013-04-03 2018-07-31 Mitsui Chemicals, Inc. Optical film
JP2017115119A (ja) * 2015-12-24 2017-06-29 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． 重合体、補償フィルム、光学フィルム及び表示装置

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KR100487701B1 (ko) 2005-05-03
US20030086027A1 (en) 2003-05-08
EP1197768A4 (fr) 2005-01-12
CN1383495A (zh) 2002-12-04
US6800697B2 (en) 2004-10-05
EP1197768A1 (fr) 2002-04-17
KR20020022725A (ko) 2002-03-27
JP4739636B2 (ja) 2011-08-03
TW533323B (en) 2003-05-21
CN1201171C (zh) 2005-05-11

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